The present invention relates to a method for the trichromatic dyeing or printing of natural and synthetic polyamide fibre materials.
The problem underlying the present invention was to find a method of dyeing or printing natural and synthetic polyamide fibre materials using dyes suitable for combination according to the trichromatic principle.
The dyeing or printing of natural and synthetic polyamide fibre mat rials according to the trichromatic principle is known. It has, however, been found that the resulting dyeings do not always fully meet the highest demands, especially in respect of brilliance and fastness to wetting and light. There is therefore a need for new dyes that can bell used in a trichromatic dyeing technique and that yield dyeings or prints which exhibit very good fastness to wetting and/or light.
It has now been found that the problem can be solved according to he invention by the method described hereinbelow. The dyeings so obtained meet the Objectives set. In particular, the dyeings obtained are distinguished by uniform colour build-up and, at the same time, constancy of shade at different concentrations and by good combinability, as well as by good fastness to wetting properties and good fastness to light,
The present invention relates to a method for the trichromatic dyeing or printing of natural or synthetic polyamide fibre material, which method comprises using at least one blue-dyeing dye of formula 
wherein
X is halogen, hydroxy, C1-C4alkoxy, Sxe2x80x94C1-C4alkyl, xe2x80x94NHR1, xe2x80x94NHR1R2, morpholino, piperidino or azepano, R1 being unsubstituted or hydroxy- or carboxy-substituted C1-C4alkyl, and R2 being unsubstituted or hydroxy-, sulfo-, carboxy- or phenyl-substituted C1-C4alkyl or phenyl,
W is xe2x80x94NR3xe2x80x94 or xe2x80x94Oxe2x80x94, R3 being hydrogen or C1-C4alkyl,
A and B are each independently of the other a cycloaliphatic or aromatic bridge member,
Q1 and Q2 are each independently of the other an anthraquinone radical, and
z is an integer 2, 3 or 4, together with at least one red-dyeing dye of formula 
wherein
R and Rxe2x80x2 are each independently of the other hydrogen or unsubstituted or substituted
C1-C4alkyl,
R5, R6, R7 and R8 are each independently of the others hydrogen, C1-C4alkyl, C1-C4alkoxy,
C2-C4alkanoylamino, ureido, halogen or sulfo, and
X1 is halogen, hydroxy, C1-C4alkoxy, Sxe2x80x94C1-C4alkyl, xe2x80x94NHR1, xe2x80x94NR1R2, morpholino, piperidino or azepano, R1 being unsubstituted or hydroxy- or carboxy-substituted C1-C4alkyl, and R2 being unsubstituted or hydroxy-, sulfo-, carboxy- or phenyl-substituted C1-C4 alkyl or phenyl, and together with at least one yellow- or orange-dyeing dye of formula 
or of formula 
wherein
R and Rxe2x80x2 are each independently of the other hydrogen or unsubstituted or substituted C1-C4alkyl,
X2 and X3 are each independently of the other halogen, hydroxy, C1-C4alkoxy, Sxe2x80x94C1-C4alkyl, xe2x80x94NHR1, xe2x80x94NR1R2, morpholino, piperidino or azepano, R1 being unsubstituted or hydroxy- or carboxy-substituted C1-C4alkyl, and R2 being unsubstituted or hydroxy-, sulfo-, carboxy- or phenyl-substituted C1-C4alkyl or phenyl, and
R9, R10, R11, R12, R13, R14, R15 and R16 are each independently of the others hydrogen, C1-C4alkyl, C1-C4alkoxy, ureido, halogen, sulfo, or C2-C4alkanoylamino or C1-C4alkoxycarbonylamino each of which is unsubstituted or substituted in the alkyl moiety.
The trichromatic principle is understood to refer to the additive colour mixing of appropriately selected yellow- or orange-, red- and blue-dyeing dyes, by means of which it is possible to obtain any desired shade of the visible colour spectrum by suitably selecting the relative proportions of the dyes.
C1-C4Alkyl that comes into consideration for R, Rxe2x80x2, R1, R2, R3, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, with preference being given to methyl or ethyl, especially methyl. Radicals R and Rxe2x80x2 as C1-C4alkyl may be unsubstituted or substituted, for example by hydroxy, C1-C4xe2x80x94alkoxy, halogen or by sulfato, but are preferably unsubstituted.
C1-C4Alkoxy that comes into consideration for R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16 and X is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy, especially methoxy.
C2-C4Alkanoylamino that comes into consideration for R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 is, for example, propionylamino or, especially, acetylamino. Radicals R9, R10, R11, R12, R13, R14, R15 and R16 as C2-C4alkanoylamino may be unsubstituted or substituted, for example, in the alkyl moiety by C1-C4alkoxy or by hydroxy.
C1-C4Alkoxycarbonylamino that comes into consideration for R9, R10, R11, R12, R13, R14, R15 and R16 is especially methoxy- or ethoxy-carbonylamino. Radicals R9, R10, R11, R12, R13, R14, R15 and R16 as C1-C4alkoxycarbonylamino may be unsubstituted or substituted, for example, in the alkyl moiety by C1-C4alkoxy or by hydroxy.
Sxe2x80x94C1-C4alkyl that comes into consideration for X, X1, X2 and X3 is, for example, methylthio, ethylthio, propylthio or butylthio.
Halogen that comes into consideration for R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, X, X1, X2 and X3 is, for example, fluorine or bromine and, especially, chlorine.
A is preferably a cyclohexylene or phenylene radical.
B is preferably a cyclohexylene or phenylene radical.
W is preferably a radical of formula xe2x80x94NR3xe2x80x94.
X1, X2 and X3 are preferably fluorine or chlorine, especially chlorine.
R and Rxe2x80x2 are preferably, each independently of the other, hydrogen or C1-C4alkyl, especially hydrogen.
R3 is preferably hydrogen.
R5, R6, R7 and R8 are preferably, each independently of the others, hydrogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, ureido or halogen, especially hydrogen.
R9, R10, R11, R12, R13, R14, R15 and R16 are preferably, each independently of the others, hydrogen, C1-C4alkyl, C1-C4alkoxy, ureido, halogen, or C2-C4alkanoylamino or C1-C4alkoxycarbonylamino each of which is unsubstituted or substituted in the alkyl moiety by C1-C4xe2x80x94alkoxy or by hydroxy.
As blue-dyeing dye there is preferably used at least one dye of formula 
wherein
Xxe2x80x2 is xe2x80x94Cl, xe2x80x94OH, xe2x80x94N(CH2CH2OH)2, xe2x80x94N(CH3)(CH2CH2SO3H), xe2x80x94NHCH2COOH, xe2x80x94N(CH2CH2CH2CH3)2, 
xe2x80x83Axe2x80x2 is a cyclohexylene or phenylene radical and
xe2x80x83Bxe2x80x2 is a cyclohexylene or phenylene radical.
As blue-dyeing dye there is especially used the dye of formula 
As blue-dyeing dye there is also especially used the dye of formula 
As red-dyeing dye there is preferably used at least one dye of formula 
wherein R, Rxe2x80x2, R5, R6, R7, R8 and X1 have the definitions and preferred meanings given above.
Especially preferred red-dyeing dyes are those of formula (2), more especially those of formula (8), wherein
R and Rxe2x80x2 are each independently of the other hydrogen or C1-C4alkyl, especially hydrogen,
R5, R6, R7 and R8 are each independently of the others hydrogen, C1-C4alkyl, C1-C4alkoxy,
C2-C4alkanoylamino, ureido or halogen, especially hydrogen, and
X1 is fluorine or, especially, chlorine.
As red-dyeing dye there is more especially used a dye of formula 
The yellow- or orange-dyeing dyes of formulae (3) and (4) preferably contain in the naphthalene rings, in each case, only one or two sulfo groups, and especially, in each case, only one sulfo group. The total number of sulfo groups of the dyes of formulae (3) and (4) is preferably in each case from two to four, especially two.
Preferred yellow- or orange-dyeing dyes of formula (3) are those of formula 
wherein R, Rxe2x80x2, R9, R10, R11, R12 and X2 have the definitions and preferred meanings given above.
Especially preferred yellow- or orange-dyeing dyes of formula (3), more especially in the form of dyes of formula (10), are those wherein
R and Rxe2x80x2 are each independently of the other hydrogen or C1-C4alkyl, especially hydrogen,
R9, R10, R11 and R12 are each independently of the others hydrogen, C1-C4alkyl, C1-C4alkoxy, ureido, halogen, or C2-C4alkanoylamino or C1-C4alkoxycarbonylamino each which is unsubstituted or substituted in the alkyl moiety by C1-C4alkoxy or by hydroxy, R9 and R11 preferably being hydrogen,
X2 is fluorine or, especially, chlorine and the naphthalene rings of the dyes of formula (3) and of formula (10) contain, in each case, only one or two sulfo groups, and especially, in each case, only one sulfo group.
More especially preferred yellow- or orange-dyeing dyes of formula (3) are those of formula 
wherein R10 and R12 have the definitions and preferred meanings given above, R10 and R12 being preferably hydrogen, C1-C4alkyl, C1-C4alkoxy, ureido, halogen, or C2-C4alkanoylamino or C1-C4alkoxycarbonylamino each of which is unsubstituted or substituted in the alkyl moiety by C1-C4alkoxy or by hydroxy, especially C1-C4alkyl, C1-C4alkoxy, ureido, halogen, or C2-C4-alkanoylamino or C1-C4alkoxycarbonylamino each of which is unsubstituted or substituted in the alkyl moiety by C1-C4alkoxy or by hydroxy, and more especially ureido.
Preferred yellow- or orange-dyeing dyes of formula (4) are those of formula 
wherein R, Rxe2x80x2, R13, R14, R15, R16 and X3 have the definitions and preferred meanings given above.
Especially preferred yellow- or orange-dyeing dyes of formula (4), more especially in the form of dyes of formula (12), are those wherein
R and Rxe2x80x2 are each independently of the other hydrogen or C1-C4alkyl, especially hydrogen,
R13, R14, R15 and R16 are each independently of the others hydrogen, C1-C4alkyl, C1-C4alkoxy, ureido, halogen, or C2-C4alkanoylamino or C1-C4alkoxycarbonylamino each of which is unsubstituted or substituted in the alkyl moiety by C1-C4alkoxy or by hydroxy, with
R13 and R15 preferably being hydrogen,
X3 is fluorine or, especially, chlorine and the naphthalene rings of the dyes of formula (4) and of formula (12) contain, in each case, only one or two sulfo groups, and especially, in each case, only one sulfo group.
Of special interest as yellow- or orange-dyeing dyes are those of formula (3), especially those of formula (10) and more especially those of formula (11).
Of very special interest as yellow- or orange-dyeing dyes are those of formula (11) wherein R10 and R12 are ureido.
A preferred embodiment of the method according to the invention comprises using at least one red-dyeing dye of formula (8) together with at least one yellow- or orange-dyeing dye of formula (3), especially of formula (10) and more especially of formula (11); for the blue-dyeing dyes of formulae (1) and (2) the definitions and preferred meanings given above apply. As blue-dyeing dye(s) there is used especially at least one of the dyes of formulae (6) and (7).
An especially preferred embodiment of the method according to the invention comprises using a red-dyeing dye of formula (9) together with at least one yellow- or orange-dyeing dye of formula (3), especially of formula (10) and more especially of formula (11); for the blue-dyeing dyes of formulae (1) and (2) the definitions and preferred meanings given above apply. As blue-dyeing dye(s) there is used especially at least one of the dyes of formulae (6) and (7).
A very especially preferred embodiment of the method according to the invention comprises using a red-dyeing dye of formula (9) together with a yellow- or orange-dyeing dye of formula (11) wherein R10 and R12 are ureido; for the blue-dyeing dyes of formulae (1) and (2) the definitions and preferred meanings given above apply. As blue-dyeing dye(s) there is preferably used at least one of the dyes of formulae (6) and (7).
The subject matter of the present invention also includes dye mixtures that comprise a mixture of at least one blue-dyeing dye of formula (1), together with at least one red-dyeing dye of formula (2) and together with at least one yellow- or orange-dyeing dye of formula (3) or (4), the definitions and preferred meanings given above applying to the dyes of formulae (1), (2), (3) and (4) and mixtures thereof.
The dyes of formula (1) are in some cases known or can be prepared in analogy to known dyes.
The dyes of formulae (6) and (7), which are covered by the generic formula (1), are new and the present invention relates also to those dyes.
The dye of formula (6) can be obtained, for example, by condensing cyanuric chloride with an amine of formula 
The dye of formula (7) can be obtained, for example, by condensing cyanuric chloride with an amine of formula 
and hydrolysing the resulting product.
For preparation of the dyes of formulae (6) and (7), the cyanuric chloride is reacted with 2 equivalents of the relevant anthraquinone compound firstly at a temperature of from xe2x88x925 to 20xc2x0 C., which is increased in the course of the reaction to about from 30 to 50xc2x0 C., the pH being kept neutral to slightly acid, preferably at a pH of from 5 to 7, by adding suitable bases, for example alkali metal bases such as lithium hydroxide or carbonate, sodium hydroxide or carbonate or potassium hydroxide or carbonate.
The dyes of formulae (2), (3) and (4) are known or can be prepared in analogy to known dyes.
Dyes of formula (2) can be obtained, for example, by condensing a cyanuric halide with the amines of formulae 
Dyes of formula (3) can be obtained, for example, by condensing a cyanuric halide with the amines of formulae 
Dyes of formula (4) can be obtained, for example, by condensing a cyanuric halide with the amines of formulae 
Preference is given to reacting the cyanuric halide firstly with an approximately stoichiometric amount of one of the two aminoazo compounds at a temperature of from xe2x88x925 to 20xc2x0 C., the pH being kept neutral to slightly acid, preferably at from 5 to 7, by adding suitable bases, for example alkali metal bases such as lithium hydroxide or carbonate, sodium hydroxide or carbonate or potassium hydroxide or carbonate. The triazine derivative obtained can be separated off or the reaction mixture can be used directly for further reaction. Advantageously, an approximately stoichiometric amount of the other of the two aminoazo compounds is added to the reaction mixture obtained or to the triazine derivative previously separated off and is reacted with the triazine derivative at a slightly elevated temperature, preferably from 30 to 50xc2x0 C., and at a neutral to slightly acid pH, preferably from 6 to 7. If the two aminoazo compounds are identical aminoazo compounds, approximately 2 equivalents of the aminoazo dye in question are reacted with 1 equivalent of the cyanuric halide, the temperature preferably being initially maintained at from xe2x88x925 to 20xc2x0 C. and then increased to about from 30 to 50xc2x0 C.
The aminoazo compounds are known or can be prepared in analogy to known compounds. For example, the azo compounds can be obtained by conventional diazotisation and coupling reactions.
The diazotisation is customarily carried out using a nitrite, for example an alkali metal nitrite such as sodium nitrite, in a mineral acid medium, for example in a hydrochloric acid medium, at temperatures of, for example, from xe2x88x925 to 30xc2x0 C. and preferably from 0 to 10xc2x0 C.
The coupling is customarily carried out at acid, neutral or slightly alkaline pH values and temperatures of, for example, from xe2x88x925 to 30xc2x0 C., preferably from 0 to 25xc2x0 C.
The dyes used in the trichromatic dyeing or printing method according to the invention are present either in their free sulfonic acid form or, preferably, in the form of a salt thereof.
Suitable salts are, for example, alkali metal, alkaline earth metal or ammonium salts or salts of an organic amine. Examples that may be mentioned are sodium, lithium, potassium or ammonium salts or a mono-, di- or tri-ethanolamine salt.
The dyes used in the method according to the invention may comprise further additives, for example sodium chloride or dextrin.
The trichromatic dyeing or printing method according to the invention can be applied to the customary dyeing and printing methods. The dye liquors or printing pastes, in addition to comprising water and the dyes, may also comprise further additives, for example wetting agents, antifoams, levelling agents or agents that influence the characteristics of the textile material, for example softeners, flame-retardant additives, or dirt-, water- and oil-repellents, and also water-softeners and natural or synthetic thickeners, for example alginates and cellulose ethers.
The trichromatic dyeing or printing method according to the invention is also suitable for dyeing from short liquors, for example in continuous dyeing methods and discontinuous or continuous foam dyeing methods.
The amounts in which the individual dyes are used in the dye baths or printing pastes can vary within wide limits depending on the required depth of shade; in general, amounts of from 0.01 to 15% by weight, especially from 0.1 to 10% by weight, based on the material to be dyed or the printing paste have proved to be advantageous.
Dyeing, especially by the exhaust process, is preferred.
Dyeing is preferably carried out at a pH of from 3 to 7, especially from 3 to 5. The liquor ratio can be selected within a wide range, for example from 1:5 to 1:50, preferably from 1:5 to 1:30. Dyeing is preferably carried out at a temperature of from 70 to 110xc2x0 C., especially from 80 to 105xc2x0 C.
When employed in trichromatic dyeing or printing, the dyes used in the method according to the invention are distinguished by uniform colour build-up, good uptake characteristics, good constancy of shade even at different concentrations, good fastness properties and solubility and, especially, by very good combinability.
The trichromatic dyeing or printing method according to the invention is suitable for dyeing or printing natural polyamide materials, for example wool, as well as, especially, synthetic polyamide materials, for example polyamide 6 or polyamide 6.6, and is suitable for dyeing or printing wool and synthetic polyamide blend fabrics or yarns.
The said textile material can be in a very wide variety of processing forms, for example in the form of fibres, yarn, woven fabrics, knitted fabrics or, especially, in the form of carpets.
Level dyeings having good all-round fastness properties, especially good fastness to rubbing, to wetting, to wet rubbing and to light, are obtained.